JP2003055175A - Hair cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a hair cosmetic causing no worry about use place and use method and capable of gradually making the grey hair inconspicuous. SOLUTION: This hair cosmetic comprises (A) an air oxidizing dye, (B) laccase and (c) a phenol or a quinone compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hair cosmetic composition which is excellent in the effect of gradually making gray hair less noticeable by a simple method of use.

[0002]

2. Description of the Related Art Generally, hair dyes such as hair nail polish and hair color are mainly used for dyeing white hair. However, hair dyes using these hair dyes have limited places of use. There was a problem that it was difficult to deal with the growing gray hair because the usage was complicated and there was a sudden change in the dyed color.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to gradually dye hair by a daily simple and convenient method of use, thereby eliminating the troublesomeness of the place of use and the method of use and making the easily grown white hair stand out. It is to provide a hair cosmetic that can be dyed without a hair.

[0004]

Means for Solving the Problems The present inventors have found that when a phenol or a quinone is combined with an air oxidation dye and laccase, the effect of making gray hair less noticeable is significantly improved. It was found that the effect is further enhanced by doing so.

That is, the present invention provides the following component (A),
(B) and (C): A hair cosmetic containing (A) an air-oxidation dye, (B) laccase, and (C) phenols or quinones.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Indole compounds or indoline compounds are preferable as the air-oxidation dye of the component (A) used in the present invention, and the indole compounds or indoline compounds are represented by the following general formula (1):

[0007]

[Chemical 2]

Examples include compounds represented by:

In the general formula (1), hydrogen is preferable as R ¹ . R ² is preferably hydrogen or a carboxyl group. Hydrogen is preferred as R ³ . Hydrogen is preferred as R ⁴ and R ⁵ .

The indoles or indolines represented by the general formula (1) include 5,6-dihydroxyindoline, 5,6-dihydroxyindole, 5,6-dihydroxyindoline-2-carboxylic acid and 5,6-dihydroxy. Indole-2-carboxylic acid is particularly preferred.

The component (A) in the hair cosmetic composition of the present invention is
It is preferably contained in an amount of 0.01 to 15% by weight (hereinafter simply referred to as%), further 0.01 to 10.0%, and particularly 0.1 to 5.0%.

The laccase of the component (B) used in the present invention is a kind of polyphenol oxidase and is obtained from plants, especially sumac sap or microorganisms such as bacteria, mold, yeast and basidiomycetes. Specific examples include Biochim. Bio
phys. Acta. 205, pp. 35-47, or ibid, 1292.
Laccase as described in Vol. 303-311 can be used. These may be used as crude enzymes or after being purified, and may be products produced by genetic engineering techniques. For example, Polyporus pincitrus (Polyp
orus pinsitus), Rhizoctonia
solani), Miseriofusora Thermohira (Myceliophtho
It is produced by microorganisms such as ra thermophila) and Citaridium thermophilum (Scytalidium thermophilum). "Laccase (EC1.1
0.3.2) "(Sigma) is commercially available.

The laccase in the hair cosmetic composition of the present invention has an enzyme activity (U) of 1 to 1 as measured by the following activity measuring method.
It is preferable to contain 000 U / g (hair cosmetic). Two or more laccases may be used in combination.

Enzyme activity measurement method 3 mL of a reaction solution containing 2 mM 5,6-dihydroxyindoline, 25 mM monosodium phosphate buffer (pH 7), 20% ethanol and laccase was prepared, and a dye formation reaction was carried out using a 1 cm thick cell. The increase in absorbance (485 nm) at 1 to 30 minutes (preferably 5 minutes) with a spectrophotometer, 2
Measure at 5 ° C. Enzyme activity (U) is 485nm for 5 minutes
It was calculated from the change in absorbance (Abs) at. (Equation 1) Enzyme unit (U) = (Abs × 3) /0.3/5

The phenols or quinones of the component (C) used in the present invention may be compounds having 1 to several hydroxyl groups on the aromatic ring, and 6 to 3 carbon atoms having 1 to 3 hydroxyl groups. Aromatic hydrocarbons of 14 (provided that they may have a substituent other than a hydroxyl group) are preferred. Examples of the basic skeleton include phenols, polyhydric phenols, naphthalene diols, and anthracene diols. Specific examples of the phenols or quinones include catechol, resorcinol, hydroquinone, pyrogallol, chloroglucinol, propyl gallate, arbutin, dibutylhydroxytoluene, juglone, naphthoquinone, futhiochol, vitamin K ₁ , vitamin K ₂ , vitamin K ₃ , Anthraquinone, anthraquinone carboxylic acid,
Examples thereof include anthraquinone sulfonic acid and anthraquinone dye. Of these, hydroquinone, catechol, dibutylhydroxytoluene and arbutin are particularly preferable.

The component (C) in the hair cosmetic composition of the present invention is 0.
The content of 01 to 1%, and further 0.05 to 0.5%,
It is preferable in terms of hair dyeing effect.

When the hair cosmetic composition of the present invention contains a film-forming polymer, a styling effect can be imparted to the hair cosmetic composition. Examples of the film-forming polymer include nonionic polymers, cationic polymers, anionic polymers and amphoteric polymers, and two or more kinds may be used in combination.
Of these film-forming polymers, acrylic acid ester /
Acrylic polymer such as methacrylic acid ester copolymer (for example, plus size L-75CB, plus size L-9540B) or N-methacryloyl N, N-dimethylammonium-α-N-methylcarboxybetaine / methacrylic acid alkyl ester Copolymers (eg Yucaformer M-75) are preferred.

The film-forming polymer is preferably contained in the hair cosmetic composition of the present invention in an amount of 0.01 to 40%, particularly 0.5 to 10%.

The composition of the present invention contains silicones in an amount of 0.05 to 2 from the viewpoint of improving the feel during application and after drying.
0%, preferably 0.1 to 10%, particularly preferably 0.5 to 5%. Two or more silicones may be used in combination.

Examples of silicones include dimethyl polysiloxane, polyether modified silicone, amino modified silicone, carboxy modified silicone, methylphenyl polysiloxane, fatty acid modified silicone, alcohol modified silicone, aliphatic alcohol modified silicone, epoxy modified silicone, and fluorine modified silicone. Examples thereof include silicone, cyclic silicone, and alkyl-modified silicone. Of these, polymethylsiloxane, polyether-modified silicone, and amino-modified silicone are preferable. When used together with polymethylsiloxane, good lubricity can be imparted to the hair, the polyether-modified silicone can impart smoothness, and the amino-modified silicone imparts a moist feeling. be able to. The polymethylsiloxane is obtained from 5 mm ² / s a viscosity (25 ° C.) in response to touch, 10 million mm ² often supplied as an emulsion
/ S can be used. Preferably 5000-100
It is preferably 100,000 mm ² / s, particularly preferably 50,000 to 10 million mm ² / s. Polyether-modified silicone is a general term for polyoxyethylene / methylpolysiloxane copolymer and poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer, and those having various HLBs are known. The silicone KF351A, KF353A and KF6008 manufactured by Shin-Etsu Chemical Co., Ltd.
Same KF6016, same KF6011, same KF6012,
SH3771C, 3 manufactured by Toray Dow Corning Co., Ltd.
773C, 3775C and the like. Griffin's HLB is 4-1 as polyether modified silicone
8 and more preferably 7 to 11 are preferable. As the amino-modified silicone, amodimethicone oil or emulsion can be used, and as an example, amodimethicone emulsion SM87 manufactured by Toray Dow Corning Co., Ltd.
04C and XF-42B19 manufactured by Toshiba Silicone Co., Ltd.
89 and the like.

Further, it is preferable that the composition contains 0.1 to 10%, preferably 0.5 to 8%, and more preferably 1 to 5% of a surfactant in order to solubilize the oil agent. In addition, the surfactant is 2
You may use together 1 or more types.

As the surfactant, alkylbenzene sulfonate, alkyl or alkenyl ether sulfate,
Alkyl or alkenyl sulfate, olefin sulfonate, alkane sulfonate, saturated or unsaturated fatty acid salt,
Alkyl or alkenyl ether carboxylic acid salts, α-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphoric acid mono- or diester type surfactants, anionic surfactants such as sulfosuccinic acid ester; imidazoline type,
Amphoteric surfactants such as carbobetaine-based, amidobetaine-based, sulfobetaine-based, hydroxysulfobetaine-based or amidosulfobetaine-based amphoteric surfactants; polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, higher fatty acid sucrose esters, Polyglycerin fatty acid ester, higher fatty acid monoethanolamide or diethanolamide, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, alkyl saccharide-based surfactant, alkylamine oxide, alkylamide amine oxide, etc. Nonionic surfactants; imidazoline ring-opening type quaternary ammonium salts, quaternary ammonium salts, mono long-chain alkyl quaternary ammonium salts, di Chain cationic surfactants such as alkyl quaternary ammonium salts and the like. As the counterion of the anionic residue of these surfactants, alkali metal ions such as sodium and potassium, calcium,
Examples thereof include alkaline earth metal ions such as magnesium, ammonium ions, and alkanolamines having 1 to 3 alkanol groups having 2 or 3 carbon atoms (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.). .
As the counterion of the cationic residue, chlorine, bromine,
Examples thereof include halogen ions such as iodine, methosulfate and saccharinate ions. Among these surfactants, especially polyoxyethylene (average 25-8
0) hydrogenated castor oil, imidazoline-based amphoteric surfactant, polyoxyalkylene (average 4 to 30) alkyl (average carbon number 12 to 18) ether, mono long-chain alkyl (average carbon number 16 to 22) quaternary ammonium salt Is preferred.

The composition may contain an oil agent in an amount of 0.1 to 20%, preferably 0.5 to 5% from the viewpoint of improving the feel after drying, and two or more kinds of oil agents may be used in combination. .

As the oil agent, squalene, squalane,
Hydrocarbons such as liquid paraffin, liquid isoparaffin, and cycloparaffin; glycerides such as castor oil, cocoa oil, mink oil, avocado oil, and ozobe oil; waxes such as beeswax, whale wax, lanolin, and carnauba wax; cetyl alcohol, oleyl Alcohols such as alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, propylene glycol and glycerin; isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, hexyl laurate, emulsified cetyl, propylene glycol monostearate, Esters such as oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, tridecyl isononanoate; capric acid, lauric acid, myristic acid, palmi Phosphate, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, isostearyl acid, higher fatty acids such as isopalmitic acid, other isostearyl glyceryl ether, polyoxypropylene butyl ether. As the oil agent, esters are preferable, and hexadecyl 2-ethylhexanoate, isononyl isononanoate, isopropyl palmitate and the like are particularly preferable. It should be noted that these are preferably contained in an amount that does not inactivate the enzyme.

The hair cosmetic composition of the present invention is produced by blending the above components in an aqueous solvent, and examples of the aqueous solvent include water, ethanol, isopropanol and the like.

Examples of the form of the hair cosmetic composition of the present invention include solutions, lotions, creams, waxes, gels, aerosol sprays and aerosol foams. In particular, it is convenient to use it by filling it into a container such as a pump spray or a pump foam, but it is most preferable to use it in the form of an aerosol spray or an aerosol foam. As the propellant for the aerosol spray, for example, fluorocarbon gas such as trichloromonofluoromethane and dichlorodifluoromethane can be used, but liquefied petroleum gas (LPG), dimethyl ether (DME), carbon dioxide gas, nitrogen gas or a mixture thereof or the like can be used. Preference is given to using LPG, DME or a mixed gas of LPG and DME. The propellant is preferably used in a hair cosmetic / propellant mixing weight ratio of 99.5 to 40 / 0.5 to 60: especially 95 to 80/5 to 20. Hair cosmetics / propellants are 5-70 / 95-30, especially 20-
It may be used as a hair spray containing a large amount of propellant in a ratio of 60/80 to 40.

[0027]

EXAMPLES Example 1 The compositions shown in Table 1 were produced. The obtained composition was applied to a white hair monitor (5.0 g for short hair), and the color difference (ΔE) of the hair before and after application was evaluated according to the following evaluation criteria. The results are shown in Table 1. In addition, ΔE was measured using a color difference meter Minolta Camera Co., Ltd. CR-200.

Dyeing power evaluation method ΔE10 or more (with considerable dyeing power): ○ ΔE5 or more and less than 10 (with dyeing power): Δ Less than ΔE5 (no dyeing power): ×

[0029]

[Table 1]

Example 2 The composition shown in Table 2 was prepared. 1 g of the obtained composition was applied to 5 g of white human hair, left at room temperature for 15 minutes, washed with water, shampooed / conditioned, and dried with a drier. Then, the dyeing power (ΔE) was measured in the same manner as in Example 1. The results are shown in Table 2. The same operation was repeated 5 and 10 times, and then the same measurement was performed. The results are also shown in Table 2.

[0031]

[Table 2]

Example 3 A hair spray having the following composition was produced by a conventional method.
The obtained hair spray was excellent in hiding white hair easily. (Component) Hair setting polymer ^{* 3} 3.0 g 5,6-dihydroxyindole 0.1 g Laccase (from Miseriofusora thermohira) 2U Ethyl alcohol Appropriate amount of catechol 0.1 g Perfume 0.05 g Ion-exchanged water 10.0 g Sodium hydroxide (pH 6 Adjusted to 0.5) Liquefied petroleum gas 50.0g Total 100.0g * 3 Plus size L-75CB (manufactured by Kyoukagaku)

Example 4 A hair foam having the composition shown below was produced by a conventional method.
The obtained hair foam was excellent for easily gradually coloring white hair. (Component) 5,6-dihydroxyindole 0.1 g Laccase (from Miseriofusora thermophila) 2U Ethyl alcohol 10.0 g Polyoxyethylene tridecyl ether ^{* 4} 0.5 g Hydroquinone 0.1 g Perfume 0.05 g Ion-exchanged water Adequate amount Sodium hydroxide (Adjusted to pH 6.5) Liquefied petroleum gas 10.0 g Total 100.0 g * 4 Softanol 90 (Nippon Shokubai Co., Ltd.)

Example 5 A hair cream having the composition shown below was produced by a conventional method.
The obtained hair cream was excellent in easily making gray hair inconspicuous. (Component) POE (40.EO) hydrogenated castor oil ^{* 5} 3.0 g polyglycerin fatty acid ester ^{* 6} 5.0 g 5,6-dihydroxyindole-2-carboxylic acid 2.0 g light liquid isoparaffin ^{* 7} 2.0 g cellulose derivative ^{* 8} 1.5g POE sodium stearyl ether phosphate ^{* 9} 0.4g Laccase (from Miseriofusora thermohira) 2U Dibutylhydroxytoluene 0.2g Cetanol 2.5g Ethanol 0.5g Perfume 0.1g Sodium hydroxide (adjusted to pH 6.5) ) Purified water Suitable amount Total 100.0 g * 5 Emulgen 320P (manufactured by Kao) * 6 Exepearl DG-MI (manufactured by Kao) * 7 Palmream 4 (manufactured by NOF Corporation) * 8 Polymer JR400 (manufactured by Union Carbide) * 9 SPE-104NB (Made by Kao)

Example 6 A hair gel having the composition shown below was produced by a conventional method. The obtained hair gel was excellent in easily making gray hair inconspicuous. (Component) Hair setting polymer 1 ^{* 10} 4.8 g 5,6-dihydroxyindodrine bromate 0.5 g Laccase (from Miseriofusora thermophila) 15U Ethyl alcohol 10.0 g Carboxyvinyl polymer ^{* 11} 0.5 g Polyoxyethylene tri Decyl ether ^{* 12} 0.5g Propyl gallate 0.5g Perfume 0.2g Ion-exchanged water Sodium hydroxide (adjusted to pH 6.5) Total 100.0g * 10 Plus size L-9540B (manufactured by Mitsubishi Petrochemical) * 11 Carbopol 981 (manufactured by BFGOODRICH) * 12 Softanol 90 (manufactured by Nippon Shokubai)

Example 7 A hair foam having the composition shown below was produced by a conventional method.
The obtained hair foam was excellent for easily and gradually dyeing gray hair. 5,6-Dihydroxyindoline-2-carboxylic acid hydrochloride 3.0 g Laccase (from Miseriophthora thermophila) 2U Ethyl alcohol 10 g Polyoxyethylene tridecyl ether 1 g Arbutin 0.5 g Perfume 0.05 g Ion-exchanged water Sodium hydroxide (pH 6) Adjusted to 0.5) Liquefied petroleum gas 10 g Total 100.0 g

[0037]

[Effects of the Invention] Gray hair can be dyed by a simple treatment,
There is no need to worry about the place of use and the method of use, and it is possible to easily and gradually make the gray hair inconspicuous.

Continued front page    (72) Inventor Kenzo Koike             Kao Stock Association 2-1-3 Bunka, Sumida-ku, Tokyo             Company research institute F-term (reference) 4C083 AB032 AB082 AC012 AC072                       AC102 AC182 AC392 AC422                       AC432 AC471 AC472 AC491                       AC492 AC851 AC852 AC902                       AD092 AD262 AD352 AD392                       AD471 AD472 BB21 CC36                       DD08 DD31 DD41 EE05 EE26

Claims (2)

[Claims] 1. A hair cosmetic containing the following components (A), (B) and (C): (A) air-oxidation dye, (B) laccase, (C) phenols or quinones. 2. The component (A) has the following general formula (1): The hair cosmetic composition according to claim 1, which is an indole or an indoline represented by.